CN102597302A - In-Ga-Zn-O oxide sintered body sputtering target having excellent stability In long-term film formation - Google Patents

In-Ga-Zn-O oxide sintered body sputtering target having excellent stability In long-term film formation Download PDF

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CN102597302A
CN102597302A CN2010800488551A CN201080048855A CN102597302A CN 102597302 A CN102597302 A CN 102597302A CN 2010800488551 A CN2010800488551 A CN 2010800488551A CN 201080048855 A CN201080048855 A CN 201080048855A CN 102597302 A CN102597302 A CN 102597302A
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sputtering target
crystal formation
target
ratio
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CN102597302B (en
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糸濑将之
矢野公规
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Idemitsu Kosan Co Ltd
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Abstract

The present invention provides a sputtering target which contains In, Zn and Ga and comprises an oxide sintered body having a surface and an internal compound with substantially the same crystal form.

Description

The In-Ga-Zn-O of the excellent in stability during long-term film forming is the oxidate sintered body sputtering target
Technical field
The present invention relates to a kind ofly to be used to make sulls such as oxide semiconductor or nesa coating, especially for the sputtering target of making thin film transistor.
Background technology
Comprise Indium sesquioxide and zinc oxide, perhaps comprise amorphous oxide film of Indium sesquioxide, zinc oxide and gallium oxide owing to have visible light permeability; And have the electric characteristic of wide region up to isolator ground from conductor, semi-conductor, therefore receive publicity as nesa coating or (used in the thin film transistor etc.) semiconductor film.
As said oxide film film; The film forming that the chemistry such as film forming or sol-gel method of physics such as sputter, pulsed laser deposition (PLD), vapor deposition are arranged; And as can be under lower temperature the even film forming method of big area, be that the center is studied with the film forming of physics such as sputtering method.
When forming sull with the film forming of physics such as sputter, for equably, stably, (with high film forming speed) film forming effectively, general way is to use the target that comprises oxidate sintered body.
As representational oxide film (conducting film semiconductor film), for example can enumerate the oxide film that comprises Indium sesquioxide, zinc oxide, gallium oxide.As the target that is used to make these oxide films (normally amorphous film) (mainly being sputtering target), with InGaZnO 4, In 2Ga 2ZnO 7Material etc. the composition of known crystal type or close with it composition is that the center is studied.
For example, in the patent documentation 1, disclose and comprise InGaZnO 4(InGaO 3The target of framework (ZnO)).In addition, in the patent documentation 2, for the high Ga of insulativity 2O 3Crystalline phase has carried out not making it the research of the manufacturing process that generates.In addition, in the patent documentation 3 and 4, the sputtering target as principal constituent with ZnO is disclosed, however the just research of optical recording medium purposes, transparency electrode purposes, and when research uses this kind target to form thin film transistor to the influence of transistor characteristic.In addition, in the patent documentation 5, studied and comprised InGaZnO 4Hexagonal crystal lamellar compound and ZnGa 2O 4The target etc. of mixture of spinel structure utilized the exploitation of target of the characteristic of mixture.But, the surface of in these researchs, not carrying out target and the research of the proterties such as crystal formation of inside or make their the consistent research of crystal formation.
In addition, in the patent documentation 6, disclose use metal ratio of components In: Ga: Zn=30: 15: 55 In-Ga-Zn-O sintered compact forms the example of non-crystal oxide semiconductor film and thin film transistor.But, do not study proterties, the method for manufacture of suitable sputtering target, if use this kind sintered compact as target, then have film Ga contain that ratio is minimum, about 2/3rds the problem that contains ratio of the Ga that is merely target.This is illustrated in the target, has very big distribution aspect the various proterties of composition comprising, yet does not study for the homogeneity of target proterties.
Making trend practicability along with the thin film transistor that has used sputtering target; With in the past use the transistorized making of silicon based thin film of the plasma body vapor growth method (PECVD) supplied with by gas different; Be to use a target to continue to carry out sputter for a long time; Thereby along with the change of the variation of the film characteristics of gained or film forming speed etc.; Thin-film transistor performance will change, thereby needs fine setting of filming condition etc., obviousization that become of the instable problem when carrying out film forming for a long time.In addition, it is obvious that, compares with the situation that forms nesa coating, is that this influence of semiconductor element of representative is especially obvious with thin film transistor (TFT).Though as stated the target that is used to make sull has been carried out various researchs, yet the stability of the performance of the film proterties of gained and even thin film transistor does not take in during for target film forming of long-time use.
TP in the past
Patent documentation
[patent documentation 1] TOHKEMY 2007-73312 communique
[patent documentation 2] TOHKEMY 2007-223849 communique
[patent documentation 3] WO2004/079038
No. 3644647 communiques of [patent documentation 4] Japanese Patent
[patent documentation 5] WO2008/072486
[patent documentation 6] TOHKEMY 2008-53356 communique
Summary of the invention
The objective of the invention is to, provide a kind of when carrying out long film forming the sputtering target of the excellent in stability of the film characteristics of gained.
In order to reach above-mentioned purpose, the inventor etc. further investigate repeatedly, and the result finds, the unstable of the film characteristics during long-time film forming be because, because of long-time lasting sputter changes the proterties (resistivity etc.) of target.Find that in addition in a single day the sputtering target that comprises Indium sesquioxide, zinc oxide and gallium oxide carries out long-time film forming, will cause the variation (variation of crystal formation) of the crystal habit of the surperficial face that receives sputter, this point becomes described instable reason.
This problem in the past at the sputtering target that comprises Indium sesquioxide and White tin oxide, comprise in the sputtering target of Indium sesquioxide and zinc oxide and not obviousization.Can infer this be because; Because of comprising gallium simultaneously and zinc contains lamellar compound; In the crystal formation that can generate, produce variety,, can crystal formation changed because of the change of the ratio of components due to the difference of slight condition or the evaporation of composition etc. because it generates the difference of temperature.
Find in addition; Through the selected method of manufacture that is suitable for obtaining suitable ratio of components, create conditions, for example, the molding that thickness is big heats up with speed slowly; Make sintered compact; Grind fully and cut the surface and process target, or adopt with respect to each and form the condition that generates appropriate crystal formation etc., just can solve.
In addition; Through use making like this, surface portion is identical with inner crystal habit (under crystal formation is two or more situation; The combination of crystal formation is identical) sputtering target, even carry out long-time film forming, the variation of film forming speed is also very little; Thereby the present invention has been accomplished in the variation of the characteristic of the TFT that the film that successfully suppresses the use gained is produced.
Find that in addition if use the present invention, then the difference of target and film composition also can diminish, thereby the ratio that contains that also can improve the Ga of film is compared the problem that becomes minimum with the ratio that contains of the Ga of target.
According to the present invention, the method for manufacture of following sputtering target and sputtering target can be provided.
1. sputtering target, it contains In, Zn, and Ga, comprises the identical in fact oxidate sintered body of crystal formation of surface and the compound of inside.
2. the sputtering target of record in above-mentioned 1, wherein, the resistivity on the surface of said oxidate sintered body (R1) is with (t is the mean thickness of sputtering target apart from surperficial t/2mm.) the ratio R1/R2 of resistivity (R2) in deep be more than 0.4 below 2.5.
3. the sputtering target of record in above-mentioned 1 or 2, wherein, the In of said oxidate sintered body, Zn, and the ratio of components (atomic ratio) of Ga satisfy any in the following ranges 1～6.
Scope 1
Ga/(In+Ga+Zn)≤0.50
0.58≤In/(In+Zn)≤0.85
In/(In+Ga)≤0.58
Scope 2
Ga/(In+Ga+Zn)≤0.50
0.20≤In/(In+Zn)＜0.58
In/(In+Ga)≤0.58
Scope 3
0.20＜Ga/(In+Ga+Zn)
0.51≤In/(In+Zn)≤0.85
0.58＜In/(In+Ga)
Scope 4
0.00＜Ga/(In+Ga+Zn)＜0.15
0.20≤In/(In+Zn)＜0.51
0.58＜In/(In+Ga)
Scope 5
0.00＜Ga/(In+Ga+Z1n)≤0.20
0.51≤In/(In+Zn)≤0.85
Scope 6
0.15≤Ga/(In+Ga+Zn)
In/(In+Zn)＜0.51
0.58＜In/(In+Ga)
4. the sputtering target of record in above-mentioned 3, wherein, said identical in fact crystal formation only is made up of a kind of crystal formation.
5. the sputtering target of record in above-mentioned 4, wherein, said a kind of crystal formation is with In 2Ga 2ZnO 7The homology crystalline structure of expression, and satisfy the ratio of components of said scope 1.
6. the sputtering target of record in above-mentioned 4, wherein, said a kind of crystal formation is with InGaO 3(ZnO) the homology crystalline structure of expression, and satisfy the ratio of components of said scope 2 or scope 3.
7. the sputtering target of record in above-mentioned 4; Wherein, Said a kind of crystal formation be in 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° crystalline structure with the Alpha-ray X-ray diffraction of Cuk peak, and satisfy the ratio of components of said scope 4.
8. the sputtering target of record in above-mentioned 3, wherein, said identical in fact crystal formation comprises with ZnGa 2O 4The expression spinel crystal structure and with In 2O 3The bixbite crystalline structure of expression, and satisfy the ratio of components of said scope 1 or scope 3.
9. the sputtering target of record in above-mentioned 3; Wherein, said identical in fact crystal formation is included in that 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° have the crystalline structure at the Alpha-ray X-ray diffraction of Cuk peak and with In 2O 3The bixbite crystalline structure of expression, and satisfy the ratio of components of said scope 5.
10. the sputtering target of record in above-mentioned 3; Wherein, said identical in fact crystal formation is included in that 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° have the crystalline structure at the Alpha-ray X-ray diffraction of Cuk peak and with InGaO 3(ZnO) the homology crystalline structure of expression, and satisfy the ratio of components of above-mentioned scope 6.
11. the method for manufacture of the sputtering target of each record in a kind above-mentioned 4,5,6 and 8 comprises the operation of following (a)～(e).
(a) the starting compound powder is prepared the operation of mixture;
(b) said mixture is shaped and prepares the operation of the molding more than the thick 6.0mm;
(c) operation that atmosphere is heated up with the heat-up rate below 3 ℃/minute;
(d) the said molding that has heated up more than 2 hours below 96 hours, is obtained the operation of the above sintered compact of thick 5.5mm at sintering below 1520 ℃ more than 1280 ℃ again;
(e) operation of cutting more than the 0.25mm is ground on the surface of said sintered compact.
12. the method for manufacture of sputtering target of above-mentioned 5 records comprises the operation of following (a)～(e).
(a) the starting compound powder is prepared the operation of mixture;
(b) said mixture is shaped and prepares the operation of the molding more than the thick 6.0mm;
(c) operation that atmosphere is heated up with the heat-up rate below 3 ℃/minute;
(d) with the said molding that has heated up again surpassing sintering below 1350 ℃ and 1540 ℃ more than 2 hours below 36 hours, obtain the operation of the above sintered compact of thick 5.5mm;
(e) operation of cutting more than the 0.25mm is ground on the surface of said sintered compact.
13. the method for manufacture of one kind above-mentioned 8 sputtering target comprises the operation of following (f)～(i).
(f) the starting compound powder is prepared the operation of mixture;
(g) said mixture is shaped and is prepared into the operation of body;
(h) operation that atmosphere is heated up with the heat-up rate below 10 ℃/minute;
(i) with the said molding that has heated up again in the operation below 96 hours more than 4 hours of sintering below 1350 ℃ more than 1100 ℃.
According to the present invention, can be provided in the sputtering target of the excellent in stability of the film characteristics of gained when carrying out long film forming.
Based on the present invention,, also can obtain stable tft characteristics even under the situation of having carried out long film forming.
Description of drawings
Fig. 1 is the synoptic diagram of the structure of expression channel stopper type thin film transistor of the present invention (reverse-staggered thin film transistor).
Embodiment
Sputtering target of the present invention (below be called target of the present invention) is characterised in that, contains In, Zn, and Ga, comprises the identical in fact oxidate sintered body of kind of surface and the crystal formation of the compound of inside.
If the surface of target is identical in fact with the kind of the crystal formation of the compound of inside, even, also can aspect the film characteristics of gained, not produce change then using a target to carry out for a long time under the film forming situation.
Here said " in fact " is meant, when measuring the face after cutting surface and inside with X-ray diffraction mensuration (XRD), the kind of the crystal formation that is identified is identical to get final product.
For the surface of target and the identical in fact situation of crystal formation of the compound of inside; For example; When average thickness is t mm; Counting t/2mm cutting from the surface, measuring crystal formation and the crystal formation of compound of counting the deep of t/2mm from the surface that (XRD) analyze the compound on surface with X-ray diffraction and judge.
For the crystalline structure on the surface of sputtering target, can directly measure target material surface with X-ray diffraction, confirm according to the X-ray diffraction spectrogram of gained.
Crystalline structure for the deep of sputtering target can flatly cut target and face, directly measures the facet of gained with X-ray diffraction, confirms according to the X-ray diffraction spectrogram of gained.
The cutting method of target is for example as follows.
Device: (strain) Maruto Million-Cutter 2MC-503N
Condition: diamond blade
Figure BDA0000158184380000061
Step:
1. will absorb version (alumina plate) and heat, be coated with Ah beans Fei Kusi (ア De Off イ Star Network ス, Maruto corporate system caking agent) in the above.
2. behind the placement target, target is fixed through water quenching.
3. will absorb version and be placed in the device, the cutting target.
4. carry out 1～3 repeatedly to form arbitrarily the mode in face of tool thereafter.
The condition determination of X-ray diffraction is for example as follows.
Device: (strain) Rigaku makes Ultima-III
X ray: Cu-K alpha-ray (wavelength
Figure BDA0000158184380000071
is with graphite monochromator monochromatization in addition)
2 θ-θ reflection method, continuous sweep (1.0 °/minute)
Sampling interval: 0.02 °
Slit DS, SS:2/3 °, RS:0.6mm
For crystal formation, can be to the crystal formation that registration is arranged in JCPDS (Joint Committee of Powder Di ffraction Standards) card, through coming specific with the contrast of JCPDS card.
If judge structure with crystalline structure X-ray diffraction spectrogram, oxygen no matter be too much or deficiency (oxygen defect) can (conform to stoichiometric ratio or depart from can) yet, preferably have oxygen defect.If hyperoxia, then resistance might become too high when processing target.
Target of the present invention is except the identical situation of crystal formation, and under the situation that contains the crystal formation more than 2 kinds, preferred peak intensity is more roughly the same than also.The peak intensity ratio relatively be recently carrying out with the height of the maximum peak of each crystal formation.The ratio of the height of maximum peak relatively, if difference for ± 30% with next be judged as roughly the same.More preferably difference be below ± 15%, be preferably especially ± below 5%.
The difference of the ratio of the height of maximum peak is more little, and then when using for a long time, the change of the film characteristics of gained is expected to more little.
Target of the present invention also can contain the metallic element beyond above-mentioned In, Ga, the Zn in the scope of not damaging effect of the present invention, for example contain Sn, Ge, Si, Ti, Zr and Hf etc.
Among the present invention, contained metallic element also can not comprise the elements in addition such as impurity that contain inevitably because of raw material or manufacturing process etc. in the target, and is merely In, Ga and Zn, or be merely In, Ga, Zn and Sn.
The crystal particle diameter on surface all is preferably below the 20 μ m with the crystal particle diameter of counting the deep of t/2mm from the surface, more preferably below the 10 μ m, is preferably especially below the 5 μ m.
If there is a great difference on the surface with the crystal particle diameter in deep, just might aspect discharging condition, produce difference.
In target of the present invention, the resistivity on the surface of oxidate sintered body (R1) and the ratio R1/R2 of counting the resistivity (R2) in the deep of t/2mm from the surface are preferably more than 0.4 below 2.5.
R1/R2 is preferably more than 0.4 below 2.5, more preferably more than 0.5 below 2, is preferably especially more than 0.67 below 1.5.
If R1/R2 is less than 0.4 or surpass 2.5; Then when the use of target begins and use for a long time and when consuming the proterties (resistivity etc.) of target can change, might become that film forming speed changes, or the instable reasons such as characteristic changing of the TFT that produces.
In the target of the present invention, the In of oxidate sintered body, Zn, and the ratio of components (atomic ratio) of Ga preferably satisfy any of following ranges 1～6.
Scope 1
Ga/(In+Ga+Zn)≤0.50
0.58≤In/(In+Zn)≤0.85
In/(In+Ga)≤0.58
Scope 2
Ga/(In+Ga+Zn)≤0.50
0.20≤In/(In+Zn)＜0.58
In/(In+Ga)≤0.58
Scope 3
0.20＜Ga/(In+Ga+Zn)
0.51≤In/(In+Zn)≤0.85
0.58＜In/(In+Ga)
Scope 4
0.00＜Ga/(In+Ga+Zn)＜0.15
0.20≤In/(In+Zn)＜0.51
0.58＜In/(In+Ga)
Scope 5
0.00＜Ga/(In+Ga+Zn)≤0.20
0.51≤In/(In+Zn)≤0.85
Scope 6
0.15≤Ga/(In+Ga+Zn)
In/(In+Zn)＜0.51
0.58＜In/(In+Ga)
The more preferred range of each scope is as follows.
Scope 1
Ga/(In+Ga+Zn)≤0.45
0.58≤In/(In+Zn)≤0.80
In/(In+Ga)≤0.56
Scope 2
Ga/(In+Ga+Zn)≤0.40
0.35≤In/(In+Zn)＜0.58
In/(In+Ga)≤0.58
Scope 3
0.20＜Ga/(In+Ga+Zn)
0.60≤In/(In+Zn)≤0.85
0.60＜In/(In+Ga)
Scope 4
0.09＜Ga/(In+Ga+Zn)＜0.15
0.35≤In/(In+Zn)＜0.48
0.58＜In/(In+Ga)
Scope 5
0.09＜Ga/(In+Ga+Zn)≤0.20
0.53≤In/(In+Zn)≤0.75
Scope 6
0.17≤Ga/(In+Ga+Zn)
0.35≤In/(In+Zn)＜0.48
0.60＜In/(In+Ga)
The further preferred range of scope 6 is as follows.
Scope 6
0.18＜Ga/(In+Ga+Zn)
0.38＜Zn/(In+Ga+Zn)≤0.50
0.35≤In/(In+Zn)＜0.48
0.60＜In/(In+Ga)
In addition, the characteristic of each scope is as follows.
Scope 1: can make the little TFT of photoelectric current
Can make the high TFT of nitration mixture patience
Can make in fact by single crystal formation (In 2Ga 2ZnO 7) target that constitutes
In the scope 1,, perhaps make it to contain micro-doping agents such as Sn, can generate In through manufacturing conditions such as adjustment sintering temperatures 2Ga 2ZnO 7Crystal formation.In addition, can in XRD, generate In 2Ga 2ZnO 7Crystal formation beyond the oxidate sintered body that can't confirm crystal formation.Through having In 2Ga 2ZnO 7Crystal formation, can utilize laminate structure to improve electroconductibility.
In the scope 1,, can make it to contain In through manufacturing conditions such as adjustment sintering temperatures 2O 3And ZnGa 2O 4Crystal formation.Through having In 2O 3And ZnGa 2O 4Crystal formation, even the thermal treatment of not carrying out in the reducing atmosphere also is easy at In 2O 3The middle oxygen defect that generates can reduce resistivity.In addition,,, perhaps do not grind and cut, be easy to make the surface consistent yet with the crystal formation of central part even it is few then to grind the amount of cutting if contain this crystal formation.Can think because this crystal formation is stable under lower temperature this.
Scope 2: can make the little TFT of photoelectric current
Can make in fact by single crystal formation (InGaZnO 4) target that constitutes
Scope 3: can make the TFT that mobility is bigger, the S value is smaller
When making TFT, photoelectric current is little
In the scope 3,, can make it to contain In through manufacturing conditions such as adjustment sintering temperatures 2O 3Crystal formation.Through having In 2O 3Crystal formation, even do not carry out the thermal treatment in the reducing atmosphere, also be easy at In 2O 3The middle oxygen defect that generates can reduce resistivity.
In the scope 3, though the ratio of In and Ga be not 1: 1 also passable, through manufacturing conditions such as adjustment sintering temperature etc., can generate with In 2Ga 2ZnO 7Perhaps InGaZnO 4The crystal formation of the homologous structure of expression.Through having the crystal formation of homologous structure, can utilize laminate structure to improve electroconductibility.
Scope 4: can make the TFT that mobility is big, the S value is little
Can make the target that constitutes by single crystal formation in fact
Be easy to reduce the resistivity of target
In the scope 4,, can make the target that constitutes by single crystal formation in fact through manufacturing conditions such as adjustment sintering temperatures.Single because of coming down to, the homogeneity of target will improve.In addition, electroconductibility improves.
Scope 5: can make the TFT that mobility is very big, the S value is little
Be easy to reduce the resistivity of target
In the scope 5, can make being included in that 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° have the crystalline structure at the Alpha-ray X-ray diffraction of Cuk peak and with In 2O 3The target of the crystal formation of expression.Utilize the combination of this crystal formation,, also be easy at In even do not carry out the thermal treatment in the reducing atmosphere 2O 3The middle oxygen defect that generates can reduce resistivity.
The thin film transistor of the high mobility that the sputtering target that in addition, has a composition of scope 5 has been suitable for obtaining the change of semiconductor layer film.
Scope 6: can make the TFT that mobility is bigger, the S value is little
(compare with scope 4, photoelectric current nitration mixture patience wet fastness is good)
In the scope 6, can make being included in that 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° have the crystalline structure at the Alpha-ray X-ray diffraction of Cuk peak and with InGaZnO 4The target of the crystal formation of expression.Utilize homologous structure that electroconductibility is improved.
When using target of the present invention to make TFT, Ga/ (In+Zn+Ga) more greatly then is expected to reduce photoelectric current more greater than 0.
In addition, Ga/ (In+Zn+Ga) is below 0.50, then is expected to improve mobility or S value more more for a short time.
When using target of the present invention to make TFT, be more than 0.20 In/(In+Zn), more greatly then be expected to improve mobility more.
In addition, In/ (In+Zn) is below 0.80, then is expected to be easy to be adjusted into normal off more and opens (normally off) more for a short time.
In Ga amount scope 1 and 2 how, when utilizing spatter film forming, because the variation of film forming speed or support density is relatively more responsive for oxygen partial pressure, therefore slight sometimes change or the uneven homogeneity or the reduction reproducibility that will upset the film characteristics of gained.
The aspect of the changing sensitivity of oxygen partial pressure is considered preferable range 3～scope 6, special preferable range 4 and scope 5 from film forming speed or support density.
In the target of the present invention, identical in fact crystal formation also can only be made up of a kind of crystal formation.
Under situation about only constituting, be expected to improve the homogeneity of target rerum natura or improve outward appearance (suppressing the generation of irregular colour or white point stain etc.) by a kind of crystal formation.In addition, also be expected to improve the intensity (bending strength or shock strength) of target sometimes.
In the target of the present invention, preferred above-mentioned a kind of crystal formation is with In 2Ga 2ZnO 7The homology crystalline structure of expression, and satisfy the ratio of components of above-mentioned scope 1.
Expression (YbFeO 3) 2The FeO type crystal structure with In 2Ga 2ZnO 7(or (InGaO 3) 2ZnO) crystalline structure of expression is known as " hexagonal crystal lamellar compound " perhaps " crystalline structure of homotype phase ", is by the crystal layer stack crystal that which floor formed has macrocyclic " natural superlattice " structure formation with different materials.Thickness at crystal cycle or each thin film layer is under the situation of nanometer degree, utilizes the chemical constitution of these layers or the combination of thickness of layer, can obtain with single material or with each layer mix equably and the inherent characteristic of different in kind of mixed crystal.In addition, for the crystalline structure of homotype phase, for example can according to the X-ray diffraction spectrogram that directly determines by the crushed material of target or cutting blades or target itself with confirm by the crystalline structure X-ray diffraction spectrogram of the homotype phase of ratio of components imagination is consistent.Specifically, can basis confirm with the crystalline structure X-ray diffraction spectrogram of the homotype phase that is obtained by JCPDS (Joint Committee of Powder Diffraction Standards) card is consistent.
With In 2Ga 2ZnO 7The crystalline structure of expression is JCPDS card No.38-1097.
This crystal formation can contain Sn (tin) and acquisition easily with following ratio of components (atomic ratio) through in the composition of scope 1.
0.005＜Sn/(In+Ga+Zn+Sn)＜0.10
The scope of above-mentioned Sn content is following ranges more preferably.
0.01＜Sn/(In+Ga+Zn+Sn)＜0.05
In order to obtain this crystal formation (with In 2Ga 2ZnO 7The homology crystalline structure of expression), sintering temperature is preferably 1350 ℃～1540 ℃, more preferably 1380～1500 ℃.
In the target of the present invention, preferred a kind of crystal formation is with InGaO 3(ZnO) the homology crystalline structure of expression, and satisfy the perhaps ratio of components of scope 3 of said scope 2.
With InGaO 3(ZnO) mThe crystalline structure of (m is 1～20 integer) expression also is " hexagonal crystal lamellar compound " perhaps " crystalline structure of homotype phase ".
With InGaO 3(ZnO) crystalline structure of expression is JCPDS card No.38-1104.
InGaO 3(ZnO) be InGaO 3(ZnO) mThe situation of the m=1 of (m is 1～20 integer), also note is made InGaZnO sometimes 4
In the target of the present invention; Preferred a kind of crystal formation be in 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° crystalline structure with the Alpha-ray X-ray diffraction of Cuk peak, and satisfy the ratio of components of said scope 4.
The oxide crystal of this crystal formation does not have in JCPDS (Joint Committee of Powder Diffraction Standards) card, is still unacknowledged so far novel crystal.
The X-ray diffraction in crystals figure of this oxide compound with InGaO 3(ZnO) 2(JCPDS:40-0252) crystalline structure of expression reaches with In 2O 3(ZnO) 2(JCPDS:20-1442) crystalline structure of expression is similar.But oxide compound of the present invention has InGaO 3(ZnO) 2Distinctive peak (peak of above-mentioned scope A), and In 2O 3(ZnO) 2Distinctive peak (peak of above-mentioned scope D and E), and have at InGaO 3(ZnO) 2And In 2O 3(ZnO) 2In the peak (above-mentioned scope B) that do not observe.So, oxide compound of the present invention and InGaO 3(ZnO) 2And In 2O 3(ZnO) 2Different.
The characteristic of this new crystal satisfies following condition 1.
Utilizing X-ray diffraction to measure among the figure that (Cuk alpha-ray) obtain, observing diffraction peak in the scope of following A～E.
Condition 1
A. input angle (2 θ)=7.0 °～8.4 ° (being preferably 7.2 °～8.2 °)
B.2 θ=30.6 °～32.0 ° (being preferably 30.8 °～31.8 °)
C.2 θ=33.8 °～35.8 ° (being preferably 34.5 °～35.3 °)
D.2 θ=53.5 °～56.5 ° (being preferably 54.1 °～56.1 °)
E.2 θ=56.5 °～59.5 ° (being preferably 57.0 °～59.0 °)
In addition, preferably satisfy following condition 2.
Condition 2
At 2 θ be 30.6 °～32.0 ° (above-mentioned scope B) and 33.8 °～35.8 ° (above-mentioned scope C) position detection to a side of diffraction peak be main peak, the opposing party is a submaximum.And said here main peak is meant the highest peak of height of maximum peak of the XRD spectra of crystal formation, and so-called submaximum is meant the peak of second largest height.
In addition, in the target of the present invention, identical in fact crystal formation also can be made up of two or more crystal formations.
In the target of the present invention, preferred identical in fact crystal formation comprises with ZnGa 2O 3The expression spinel crystal structure and with In 2O 3The bixbite crystalline structure of expression, and satisfy the ratio of components of above-mentioned scope 1 or scope 3.
Through possessing with ZnGa 2O 4The spinel crystal structure of expression is expected to suppress the Ga as isolator 2O 3Generation.In case generate Ga as isolator 2O 3, the frequency gets higher of paradoxical discharge, the resistance of target are uprised etc.
Through containing with In 2O 3The bixbite crystalline structure of expression is not easy to make the low target of resistivity even do not reduce to handle yet.
The oxygen containing ratio of other parts around the oxygen containing ratio of the tissue that the content of In is many preferably is lower than.The oxygen containing ratio of each tissue can distribute through the composition based on electro-probe micro analyzer (EPMA) and confirm.
In addition, with In 2O 3The lattice parameter a of the bixbite structure of expression is preferably below 10.14, more preferably below 10.10, is preferably below 10.08 especially.Utilize the match of XRD to obtain lattice parameter a.If lattice parameter is little, utilize the raising of mobility to reduce resistivity with regard to being expected to.
This crystal formation (comprising spinel crystal structure and bixbite crystalline structure) is expected to through with the composition of scope 1 or scope 3, obtain at 1100 ℃～1350 ℃ of sintering etc.
If can generate this crystal formation,, the situation that can make the surface sputtering target identical in fact with the kind of the crystal formation in deep is arranged also even grind when cutting less than 0.3mm on when then the mean thickness of oxidate sintered body is less than 5.5mm or the surface of sintered compact.
In the target of the present invention, preferred identical in fact crystal formation is included in that 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° have the crystalline structure at the Alpha-ray X-ray diffraction of Cuk peak and with In 2O 3The bixbite crystalline structure of expression, and satisfy the ratio of components of said scope 5.
Through containing with In 2O 3The bixbite crystalline structure of expression is not easy to make the low target of resistivity even do not reduce to handle yet.
The oxygen containing ratio of other parts around the oxygen containing ratio of the tissue that the content of preferred In is many is lower than.The oxygen containing ratio of each tissue can distribute through the composition based on electro-probe micro analyzer (EPMA) and confirm.
In addition, with In 2O 3The lattice parameter a of the bixbite structure of expression is preferably below 10.14, more preferably below 10.10, is preferably below 10.08 especially.Can utilize the match of XRD to obtain lattice parameter a.If lattice parameter is little, then be expected to reduce resistivity because of the raising of mobility.
In the target of the present invention, preferred identical in fact crystal formation is included in that 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° have the crystalline structure at the Alpha-ray X-ray diffraction of Cuk peak and with InGaO 3(ZnO) the homology crystalline structure of expression, and satisfy the ratio of components of above-mentioned scope 6.
Through containing the new crystal that is estimated as aforesaid homology crystalline structure simultaneously and with InGaO 3(ZnO) the homology crystalline structure of expression is expected to obtain effects such as following, that is, when using as target, the change of film forming speed is few, the generation of hickie less and outward appearance is good, the bending strength height, paradoxical discharge is few.
Below, the method for manufacture of first sputtering target of the present invention (below be called first method of manufacture of the present invention) is described.
First method of manufacture of the present invention is characterised in that, comprises the operation of following (a)～(e).
(a) the starting compound powder is prepared the operation of mixture;
(b) said mixture is shaped and prepares the operation of the molding more than the thick 6.0mm;
(c) operation that atmosphere is heated up with the heat-up rate below 3 ℃/minute;
(d) the said molding that has heated up more than 2 hours below 96 hours, is obtained the operation of the above sintered compact of thick 5.5mm at sintering below 1520 ℃ more than 1280 ℃ again;
(e) operation of cutting more than the 0.25mm is ground on the surface of said sintered compact.
First method of manufacture of the invention described above is very useful for the following target in the middle of the said target of the present invention of manufacturing, that is, identical in fact crystal formation is made up of a kind of crystal formation, and this a kind of crystal formation is with In 2Ga 2ZnO 7The homology crystalline structure of expression, and satisfy the target of the ratio of components of said scope 1; A kind of crystal formation is with InGaO 3(ZnO) the homology crystalline structure of expression, and satisfy the target of the ratio of components of said scope 2; And identical in fact crystal formation comprises with ZnGa 2O 3The expression spinel crystal structure and with In 2O 3The bixbite crystalline structure of expression, and satisfy the target of the ratio of components of said scope 1 or scope 3; And identical in fact crystal formation is included in that 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° have the crystalline structure at the Alpha-ray X-ray diffraction of Cuk peak and with In 2O 3The bixbite crystalline structure of expression, and satisfy the target of the ratio of components of said scope 5.
The mean thickness of molding as a rule is more than the 6.0mm, to be preferably more than the 8mm.If more than the 6.0mm, the temperature that then is expected in the minimizing face is uneven, changes being difficult to produce aspect the kind of surface and the crystal formation in deep.
Heat-up rate as a rule is below 3.0 ℃/minute, is preferably below 2.5 ℃/minute, is preferably especially below 1.5 ℃/minute.And the lower value of heat-up rate is about 0.3 ℃/minute.If less than 0.3 ℃/minute, sintering time that then can overspending, thus might cause cost to increase.
If heat-up rate surpasses 3 ℃/minute, then the surface might change with the kind of the crystal formation in deep.Can think because the thickness direction generation temperature at target is unequal when heating up this.
Sintering temperature as a rule is more than 1280 ℃ below 1520 ℃, is preferably more than 1300 ℃ below 1500 ℃.
Sintering time as a rule is more than 2 hours below 96 hours, is preferably more than 4 hours below 48 hours, more preferably more than 6 hours below 24 hours.
Grinding the degree of depth of cutting as a rule is more than the 0.25mm, to be preferably more than the 0.3mm, more preferably more than the 0.5mm, is preferably more than the 2mm especially.If less than 0.25mm, then might remove the change part of the crystalline structure of near surface fully.
Second method of manufacture of the present invention is characterised in that, comprises the operation of following (a)～(e).
(a) the starting compound powder is prepared the operation of mixture;
(b) said mixture is shaped and prepares the operation of the molding more than the thick 6.0mm;
(c) operation that atmosphere is heated up with the heat-up rate below 3 ℃/minute;
(d) with the said molding that has heated up again surpassing sintering below 1350 ℃ and 1540 ℃ more than 2 hours below 36 hours, obtain the operation of the above sintered compact of thick 5.5mm;
(e) operation of cutting more than the 0.25mm is ground on the surface of said sintered compact.
Second method of manufacture of the present invention is very useful for the following target in the middle of the target of making the invention described above, that is, identical in fact crystal formation is made up of a kind of crystal formation, and this a kind of crystal formation is with In 2Ga 2ZnO 7The homology crystalline structure of expression, and satisfy the ratio of components of said scope 1.
Sintering temperature as a rule is to surpass below 1350 ℃ and 1540 ℃, is preferably 1380～1510 ℃, more preferably 1400～1490 ℃.If sintering temperature is below 1350 ℃ or surpasses 1540 ℃, then might become above-mentioned crystal formation (with In 2Ga 2ZnO 7The homology crystalline structure of expression) in addition crystal formation.
In addition, sintering time as a rule is more than 2 hours below 36 hours, is preferably 4～24 hours, more preferably 8～12 hours.If sintering time surpasses 36 hours, then might become above-mentioned crystal formation (with In 2Ga 2ZnO 7The homology crystalline structure of expression) in addition crystal formation.
For other condition, identical with first method of manufacture of the present invention, therefore here omit.
The 3rd method of manufacture of the present invention is characterised in that, comprises the operation of following (f)～(i).
(f) the starting compound powder is prepared the operation of mixture;
(g) said mixture is shaped and is prepared into the operation of body;
(h) operation that atmosphere is heated up with the heat-up rate below 10 ℃/minute;
(i) with the said molding that has heated up again in the operation below 96 hours more than 4 hours of sintering below 1350 ℃ more than 1100 ℃.
Very useful the following target of the 3rd method of manufacture of the present invention in the middle of making said target of the present invention, that is, identical in fact crystal formation comprises with ZnGa 2O 3The expression spinel crystal structure and with In 2O 3The bixbite crystalline structure of expression, and satisfy the ratio of components of said scope 1 or scope 3.
Heat-up rate as a rule is below 10 ℃/minute, is preferably below 6 ℃/minute, more preferably below 3 ℃/minute.If heat-up rate surpasses 10 ℃/minute, then might make surface portion and inner proterties such as crystal formation change, perhaps in target, crack.And the lower value of heat-up rate is about 0.3 ℃/minute.
Sintering temperature as a rule is more than 1100 ℃ below 1350 ℃, is preferably more than 1200 ℃ below 1300 ℃.If less than 1100 ℃, then specific density might not can improve or might be in sintering spended time.If surpass 1350 ℃, then can generate other crystal formations that at high temperature generate, might stably obtain above-mentioned crystal formation (with ZnGa 2O 3The spinel crystal structure of expression reaches with In 2O 3The bixbite crystalline structure of expression).
Sintering time as a rule is more than 4 hours below 96 hours, is preferably more than 4 hours below 48 hours, more preferably more than 6 hours below 24 hours.If less than 4 hours, then specific density might not can improve.If more than 96 hours, the change that the part evaporation of then forming may produce ratio of components, overspending time and be difficult to realize industriallization in the mill in addition.
For other condition, identical with of the present invention first or second method of manufacture, therefore here omit.
< explanation of each manufacturing process of target >
(1) compounding operation
Compounding operation is with the MOX blended operation as the raw material of sputtering target.
As raw material, use the powder of indium compound, the powder of gallium compound, the powder such as powder of zn cpds.The specific surface area (BET specific surface area) of each metallic compound that becomes the raw material of target can utilize the method for record among the JIS Z 8830 to measure.As the compound of indium, for example can enumerate Indium sesquioxide, indium hydroxide etc.As gallium compound, for example can enumerate gallium oxide, Gallium trihydroxide etc.As the compound of zinc, for example can enumerate zinc oxide, zinc hydroxide etc.As each compound, consider preferred oxides from the remaining difficulty of the easy property of agglomerating, by product.In addition, preferably use metallic zinc (zinc end) as part of raw materials.If in part of raw materials, use the zinc end, then can reduce the generation of hickie.
In addition, the purity of raw material as a rule is more than the 2N (99 quality %), is preferably more than the 3N (99.9 quality %), is preferably especially more than the 4N (99.99 quality %).If purity is lower than 2N, thus then might reduce gained the film weather resistance, when being used for liquid-crystal display, sneak into impurity and cause after image at liquid crystal side.
Used raw materials mix in the manufacturing with targets such as MOXs is preferably used common mixing kibbler, for example uses wet-type ball mill or ball mill or ultrasonic unit, mixes equably and pulverizes.
(2) pre-burning operation
The pre-burning operation be behind the mixture that obtains as the compound of the raw material of sputtering target, the operation that is provided with as required of this mixture of pre-burning.
If carry out pre-burning, improve density easily, thereby preferred, however might cause cost to rise.Thus, more preferably do not carry out pre-burning and improve density.
In the pre-burning operation, preferably under 500～1200 ℃, 1～100 hour condition with the mixture thermal treatment of MOX.This be because, less than 500 ℃ or less than 1 hour heat-treat condition under, the thermolysis that has indium compound or zn cpds, a tin compound is situation fully inadequately.On the other hand also because above under 1200 ℃ the situation or, have the situation of thickization that causes particle above under 100 hours the situation in heat-treat condition.
So, particularly preferably be, under 800～1200 ℃ TRs, 2～50 hours condition, heat-treat (pre-burning).
And the pre-burning thing that obtains was here preferably pulverized before following forming process and firing process.
(3) forming process
Forming process is the mixture of MOX (being the pre-burning thing under the situation that is provided with above-mentioned pre-burning operation) press molding to be processed the operation of molding.Utilize this operation, be configured as the shape that is suitable for as target.Under the situation that is provided with the pre-burning operation, can be after micropowder granulation with the pre-burning thing of gained, utilizing is shaped is processed into and forms required shape.
Handle as operable shaping in this operation; For example can enumerate drawing (uniaxial pressing), die forming, casting forming, injection forming etc.; Yet, preferably utilize isostatic cool pressing (CIP) to wait and be shaped in order to obtain the high sintered compact of sintered density (target).
In addition, if after drawing (uniaxial pressing), carry out isostatic cool pressing (CIP), hot isostatic pressing (HIP) etc., above forming process of 2 stages being set, is preferred improving on the reproducibility this point then.
Under the situation of using CIP (isostatic cool pressing, or hydrostatic pressurizing device), preferably with 800～4000kgf/cm 2Surface pressure kept 0.5～60 minute.More preferably with 2000～3000kgf/cm 2Surface pressure kept 2～30 minutes.In addition, if surface pressure less than 800kgf/cm 2, the density after then might sintering can not improve or resistance uprises.If surface pressure surpasses 4000kgf/cm 2, then device becomes excessive, and it is uneconomical to become.If the hold-time is less than 0.5 minute, the density after then might sintering can not improve or resistance uprises.If surpass 60 minutes, then can the overspending time, might cause uneconomical.
And, when being shaped processing, also can using Z 150PH or methylcellulose gum, gather shaping additives such as wax, oleic acid.
(4) sintering circuit
Sintering circuit is the operation that the molding that utilizes above-mentioned forming process to obtain is burnt till.
As the sintering condition under this situation, preferably add to depress and carry out at oxygen atmosphere or oxygen.If sintering in the atmosphere that does not contain oxygen then can't improve the density of the target of gained fully, thereby have the situation of the generation of the paradoxical discharge in the time of can't suppressing sputter fully.
When sintering, heat up with the heat-up rate of the atmosphere of said regulation.In addition, also can in the way of heating up, temporarily stop to heat up and keeping temperature to keep, with 2 stages with on carry out sintering.
In addition, the cooling rate of the atmosphere when burning till (speed of cooling) as a rule is below 4 ℃/minute, is preferably below 2 ℃/minute, more preferably below 1 ℃/minute, further is preferably below 0.8 ℃/minute, is preferably especially below 0.5 ℃/minute.If below 4 ℃/minute, then be easy to obtain required crystal formation of the present invention.In addition, when cooling, be difficult to crack.
(5) reduction operation
The reduction operation is the operation of handling, be provided with as required of reducing in order to reduce the body resistance utilize the sintered compact that above-mentioned sintering circuit obtains as overall target.
As adaptable method of reducing in this operation, for example can enumerate by the method for reducing gas or by reduction of vacuum firing or rare gas element etc.
Under situation about handling, can use the mixed gas of hydrogen, methane, carbon monoxide or these gas and oxygen etc. by the reduction of reducing gas.
Under situation about handling, can use the mixed gas of nitrogen, argon gas or these gas and oxygen etc. by the reduction of burning till in the rare gas element.
Among the present invention, preferably do not reduce processing (thermal treatment under inert gas atmosphere, hydrogen atmosphere or vacuum such as argon gas or nitrogen or the low pressure).In case reduce processing, just might produce or amplify the difference of the resistance value in surface element and deep.
(6) manufacturing procedure
Manufacturing procedure is to be used for the further cut of sintered compact that sintering as described above obtains is the shape that is suitable on sputter equipment, installing and backboard etc. is installed the operation of setting as required with anchor clamps is installed.
In order oxidate sintered body to be processed the sputtering target blank, preferably this sintered compact for example being used surface grinding machine to grind and cuts and make surface roughness Ra is below the 5 μ m.The surface roughness Ra of preferred target blank is below the 0.5 μ m, possesses the bevel that grinds that does not have directivity.If Ra is greater than 0.5 μ m or in abrasive surface, have directivity, then might causes paradoxical discharge or produce particle.
Here, preferred further to the sputter face enforcement mirror finish of sputtering target, average surface roughness Ra is made as below 1000 dusts.This mirror finish (grinding) can use grinding, chemical grinding, the mechanochemistry of machinery to grind known grinding techniques such as (also using of the grinding of machinery and chemical grinding).For example, can be through (polishing fluid: it is above or with free abrasive shredder (abrasive substance: SiC lapping paste etc.) after the grinding, abrasive substance is replaced by diamond paste grinds and obtain water) to be finished to #2000 with the fixed abrasive material polishing machine.
Preferably the diamond wheel to No. 200～10000, surface by utilizing carries out precision work, especially preferably utilizes 400～No. 5000 diamond wheel to carry out precision work.If use less than No. 200, or, target is broken easily greater than No. 10000 diamond wheel.
Be not particularly limited for this kind Ginding process.The sputtering target blank of gained is bonded on the backboard.
The thickness of target blank is 2～20mm as a rule, is preferably 3～12mm, is preferably 4～6mm especially.In addition, also can a plurality of targets be installed on the backboard, be made as a target in fact.
Then, in peace and quiet processing, can use air blowing or flowing water cleaning etc.Utilize to blow when removing foreign matter,, then can more effectively remove if carry out air-breathingly with suction cleaner from the opposite of nozzle.And, owing in above air blowing or flowing water cleaning, have the limit, therefore also can carry out ultrasonic cleaning etc. again.The effective means of this ultrasonic cleaning is that multiple exciting ground carries out between frequency 25～300KHz.For example can between frequency 25～300KHz, carry out ultrasonic cleaning with 12 kinds of frequencies of the multiple exciting of the spacing of 25KHz.
And the ratio of components of produced target (atomic ratio) can utilize by the analysis of induction plasma apparatus for analyzing luminosity (ICP-AES) and obtain.
[embodiment]
Below, use embodiment that the present invention is explained more specifically, yet the present invention does not receive any qualification of these embodiment.
Embodiment 1
(1) making of target
At the identical oxidate sintered body of making simultaneously under the following condition more than 2, use (cutting is also estimated) as rupture test with 1.
(a) raw material
In 2O 3Purity 4N, Asia rerum natura material (strain) system
Ga 2O 3Purity 4N, Asia rerum natura material (strain) system
ZnO purity 4N, high-purity chemical (strain) system
(b) mix: mixed 24 hours with ball mill.
(c) granulation: seasoning
(d) be shaped:
Drawing, surface pressure 400kgf/cm 2, kept 1 minute
CIP (hydrostatic pressurizing device), surface pressure 2200kgf/cm 2, kept 5 minutes
(e) sintering: electric furnace
(f) aftertreatment: do not carry out the thermal treatment (reduction is handled) under the reductive condition.
(g) processing: the sintered compact of thick 6mm ground to cut to grind be thick 5mm.
And, cut top and bottom, side with diamond custting machine, grind with surface grinding machine and cut the surface, processing surface roughness Ra is the target blank below the 5 μ m.
(h) target of gained is measured purposes in the cutting of the position of thick 2.5mm with 1 in the sintered compact as the deep.
(i) target of gained is blown with the surface of sintered compact, carry out 3 minutes ultrasonic cleaning again after, be bonded on the anaerobic backboard made of copper and process target with the indium scolder.The surface roughness Ra of target is below the 0.5 μ m, possesses the bevel that grinds that does not have directivity.
(2) target is with the evaluation of sintered compact
Utilize following method to carry out of the evaluation of the target of gained with sintered compact.
(a) resistivity
Use resistivity meter (Mitsubishi Chemical's (strain) system, Loresta) to measure based on four probe method (JIS R1637), with the MV at position, 10 place as resistivity value.According to the target of gained resistivity (R1) and inner resistivity (R2), calculate than (R1/R2) with the sintered compact surface.
(b) X-ray diffraction is measured (XRD)
Under following condition, directly measure target with sintered compact and cutting blade thereof, determine crystal formation.
Device: (strain) Rigaku makes Ultima-III
X ray: Cu-K alpha-ray (wavelength
Figure BDA0000158184380000222
is with graphite monochromator monochromatization in addition)
2 θ-θ reflection method, continuous sweep (1.0 °/minute)
Sampling interval: 0.02 °
Slit DS, SS:2/3 °, RS:0.6mm
Through contrasting to confirm the crystal formation of compound contained in the oxidate sintered body with the JCPDS card shown in the table 3.
(c) particle diameter (μ m)
With the particle diameter of electro-probe micro analyzer (EPMA) mensuration oxide crystal, in table 1, represent with median size.
(d) ratio of components (atomic ratio)
From target, gather sample, obtain atomic ratio with induction plasma apparatus for analyzing luminosity (ICP-AES) analysis.
Identity for crystal formation; To the crystal formation that identifies with XRD; To be judged to be " same " less than the situation of the crystal formation that only in a side, contains (crystal formation that is identified is all consistent); The situation that has the crystal formation that only in a side, contains is judged to be " not same " (as long as satisfy aforementioned condition, then also being judged as same at (about ± 50%) that there are differences aspect the peak intensity).
In addition, for target with sintered compact surface and inner elementary composition identity than (atomic ratio), then be to each metallic element will ± 0.01 with interior be judged as same.
For the identity of target, all be to be judged as same with interior situation 5 μ m with the surperficial and inner particle diameter of sintered compact.
For the identity of target with sintered compact surface and inner resistivity, will ± 50% with interior be judged as same.
For the identity of elementary composition ratio, be from the surface and sample is gathered in inner (surface after the cutting), analyze and compare that ratio of components (atomic ratio) judges with the icp analysis method.
(3) making of TFT
The sputtering target that has been used to complete, the channel stopper type thin film transistor (reverse-staggered thin film transistor) of construction drawing 1 also estimates.
Substrate 10 has used glass substrate (Corning 1737).At first, on substrate 10, utilize the electron beam evaporation plating method, stack gradually the Al of the Mo of thick 10nm, thick 80nm and the Mo of thick 10nm.Stacked film is used photolithography and peels off method, form gate electrode 20.
On gate electrode 20 and substrate 10, utilize the TEOS-CVD method to form the SiO of thick 200nm 2Film forms gate insulation layer 30.And the film forming of gate insulation layer also can be utilized sputtering method, yet preferably utilizes CVD methods such as TEOS (tetraethoxysilane)-CVD method or plasma chemistry vapor growth method (PECVD) method to form.If the sputter rule might make turn off current uprise.
Next, utilize the RF sputtering method, use the target of making in above-mentioned (1), form the semiconductor film 40 (channel layer) of thick 50nm.Thereafter, in atmosphere with 300 ℃ of thermal treatments 60 minutes.
On semiconductor film 40, utilize sputtering method to pile up SiO as etch stopper 60 (protective membrane) 2Film.And the protective membrane film also can be the CVD method.
In the present embodiment, will drop into RF power and be made as 200W.Atmosphere during film forming is total pressure 0.4Pa, and the gas flow ratio of this moment is Ar: O 2=95: 5.In addition, substrate temperature is 50 ℃.Utilize photolithography and etching method to be processed as suitable size with piling up the oxide semiconductor film and the protective membrane that.
After forming etch stop layer 60, stack gradually the Al of the Mo of thick 5nm, thick 50nm and the Mo of thick 5nm, utilize photolithography and dry-etching, form source electrode 50 and drain electrode 52.
Thereafter, with 300 ℃ of thermal treatments 60 minutes, obtaining channel length was that 20 μ m, channel width are the transistor of 20 μ m in atmosphere.
(4) evaluation of TFT
Implemented the evaluation of thin film transistor as followsly.
(a) mobility (field-effect mobility (μ))
Use analyzing parameters of semiconductor appearance (Keithley4200), under room temperature, shading environment, measure.
(b) S value (V/decade)
Use analyzing parameters of semiconductor appearance (Keithley4200), under room temperature, shading environment, measure.
(c) nitration mixture patience
(i) evaluation of nitration mixture patience is with the making of simple and easy element
Use shadow mask to produce simple and easy element.On the silicon substrate that has heat oxide film (100nm), set up the shadow mask that semiconductor layer forms usefulness, under the condition identical, form semiconductor film with above-mentioned (3).Set up the shadow mask that source-drain electrode forms usefulness then, utilize sputter with the gold electrode film forming, process source-drain electrode, the nitration mixture patience evaluation that forms channel length (L) 200 μ m, channel width (W) 1000 μ m is with simple and easy element (TFT).
The (ii) evaluation of nitration mixture patience
The nitration mixture patience evaluation that can confirm to drive is descended drying 15 minute with dry air and at 150 ℃ with simple and easy element (TFT) dipping in nitration mixture (phosphoric acid be the aqueous solution, 30 ℃) after 10 seconds, measures the TFT characteristic thereafter.To under gate voltage (Vg) 15V, drain voltage (Vd) 15V, can confirm the A that is evaluated as to the leakage current more than the 10-6A (Id), that can't confirm is evaluated as B, estimates with 2 stages.
(d) evaluation of photoelectric current
Relatively under the rayed with the shading environment under mensuration, with the change of threshold voltage (Vth) the A that is evaluated as,, estimate with 2 stages the B that is evaluated as more than the 2V less than 2V.
(5) evaluation of the stability the during life-time service of sputtering target
(a) stability of film forming speed (change)
The film forming speed that has compared 1000 hours continuous discharge (film forming) front and back.
With change less than 5% the A that is evaluated as, with more than 5% and less than 10% the B that is evaluated as, with the C that is evaluated as more than 10%.
Film forming speed (sputtering rate) is to remove with film formation time through the thickness that will use contact pin type surface shape measuring device Dectak (Ulvac (strain) corporate system) to determine to obtain.
(b) stability of TFT characteristic (change)
Make TFT 1000 hours continuous discharge (film forming) front and back, estimated the change of TFT characteristic (making current).With change less than 10% the A that is evaluated as, with more than 10% and less than 20% the B that is evaluated as, with the C that is evaluated as more than 20%.
(6) other
Utilization is based on the composition Determination of distribution of electro-probe micro analyzer (EPMA), can confirm that surface, deep all are to be rich in the part of indium and to compare oxygen level on every side few.
Use the film of likewise making to estimate the difference with the ratio of components of target.Ratio of components utilizes the icp analysis method to analyze and obtain.Target and film ratio of components roughly the same (ratio of components of each element of film be target each element ratio of components ± 2% in).
Embodiment 2～9 and comparative example 1～8
Except be made as the composition shown in table 2-1 and the table 2-2 and the condition, make, estimated oxidate sintered body, sputtering target and TFT with embodiment 1 identically.The result is shown among 2-1 and the table 2-2.
And, embodiment 3 and after in the reference example 1～3,5 and 6 stated used Sn compound as follows.
SnO 2Purity 4N, high-purity chemical (strain) system
And, among the embodiment 8, the In that obtains according to XRD 2O 3The lattice parameter of bixbite structure be lattice parameter a=10.074.
Embodiment 10 and 11
Owing under the situation of making, can become normally closed closing (normally on), therefore semiconductor film is made as 15nm and produce TFT with semiconductor film 50nm.Except the semi-conductor thickness is made as 15nm, adopts the composition shown in the table 2-1 and beyond the condition, make identically, estimated oxidate sintered body, sputtering target and TFT with embodiment 1.The result is shown among the 2-1.
And, utilize mensuration by EPMA, can confirm that surface, deep all are the many tissues of the content of In of embodiment 10 and 11 with to compare oxygen level on every side few.
In addition, utilize mensuration, can confirm that surface, deep all are the many tissues of the content of In of embodiment 3 with to compare tin (Sn) content on every side many by EPMA.
Reference example 1～6
Among the table 2-3, express the reference example of the sintered compact that does not contain Ga.Can know that the sintered compact that Ga is not arranged is difficult to cause the change of crystal formation of the thick direction of target.Can confirm that according to this result the such problem of permanent stability of the present invention is that tangible problem becomes (containing as raw material under the situation of sputtering target of Indium sesquioxide, gallium oxide and zinc oxide) under the situation of the sintered compact that contains Ga.
The target of making in embodiment 1 and the comparative example 1 is shown in the table 1 than (atomic ratio), particle diameter and resistivity with the elementary composition of sintered compact.
The target of making in embodiment, comparative example and the reference example is shown among 2-1～2-3 with various characteristics of sintered compact and TFT etc.And " Δ " in the crystal formation of target is meant trace ingredients (height of impurity component, main peak is below 50% of height of the main peak of principal constituent).
The contrast table of crystal formation and JCPDS card No. is shown in Table 3.
Figure BDA0000158184380000271
Figure BDA0000158184380000281
Figure BDA0000158184380000291
Figure BDA0000158184380000301
[table 3]
* new crystal:
In 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° crystalline structure with the Alpha-ray X-ray diffraction of Cuk peak
Utilizability in the industry
According to the present invention, can be provided in the sputtering target of the excellent in stability of the film characteristics of gained when carrying out long film forming.
According to the present invention, the thin film transistor with stable TFT characteristic can be provided effectively.
Though in above-mentioned explanation, specified several embodiments of the present invention and/or embodiment; Yet those skilled in the art are easy to substantially not break away from the scope of new enlightenment of the present invention and effect, and these are applied a lot of changes as illustrative embodiment and/or embodiment.So these a lot of changes are contained in the scope of the present invention.
The content of the document of putting down in writing in this specification sheets is all referred in this specification sheets.

Claims (13)

1. a sputtering target is characterized in that, contain In, Zn, reach Ga,
The identical in fact oxidate sintered body of crystal formation that comprises surperficial with inner compound.
2. sputtering target according to claim 1, wherein, the resistivity R1 on the surface of said oxidate sintered body and ratio R1/R2 apart from the resistivity R2 in the deep of surperficial t/2mm are more than 0.4 below 2.5, said t is the mean thickness of sputtering target.
3. sputtering target according to claim 1 and 2, wherein, the atom ratio of components of the In of said oxidate sintered body, Zn and Ga satisfies any in the following ranges 1～6,
Scope 1
Ga/(In+Ga+Zn)≤0.50
0.58≤In/(In+Zn)≤0.85
In/(In+Ga)≤0.58
Scope 2
Ga/(In+Ga+Zn)≤0.50
0.20≤In/(In+Zn)＜0.58
In/(In+Ga)≤0.58
Scope 3
0.20＜Ga/(In+Ga+Zn)
0.51≤In/(In+Zn)≤0.85
0.58＜In/(In+Ga)
Scope 4
0.00＜Ga/(In+Ga+Zn)＜0.15
0.20≤In/(In+Zn)＜0.51
0.58＜In/(In+Ga)
Scope 5
0.00＜Ga/(In+Ga+Zn)≤0.20
0.51≤In/(In+Zn)≤0.85
Scope 6
0.15≤Ga/(In+Ga+Zn)
In/(In+Zn)＜0.51
0.58＜In/(In+Ga)。
4. sputtering target according to claim 3, wherein, said identical in fact crystal formation only is made up of a kind of crystal formation.
5. sputtering target according to claim 4, wherein, said a kind of crystal formation is with In 2Ga 2ZnO 7The homology crystalline structure of expression, and satisfy the ratio of components of said scope 1.
6. sputtering target according to claim 4, wherein, said a kind of crystal formation is with InGaO 3(ZnO) the homology crystalline structure of expression, and satisfy the ratio of components of said scope 2 or scope 3.
7. sputtering target according to claim 4; Wherein, Said a kind of crystal formation be in 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° crystalline structure with the Alpha-ray X-ray diffraction of Cuk peak, and satisfy the ratio of components of said scope 4.
8. sputtering target according to claim 3, wherein, said identical in fact crystal formation comprises with ZnGa 2O 4The expression spinel crystal structure and with In 2O 3The bixbite crystalline structure of expression, and satisfy the ratio of components of said scope 1 or scope 3.
9. sputtering target according to claim 3; Wherein, said identical in fact crystal formation is included in that 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° have the crystalline structure at the Alpha-ray X-ray diffraction of Cuk peak and with In 2O 3The bixbite crystalline structure of expression, and satisfy the ratio of components of said scope 5.
10. sputtering target according to claim 3; Wherein, said identical in fact crystal formation is included in that 2 θ=7.0 °～8.4 °, 30.6 °～32.0 °, 33.8 °～35.8 °, 53.5 °～56.5 ° and 56.5 °～59.5 ° have the crystalline structure at the Alpha-ray X-ray diffraction of Cuk peak and with InGaO 3(ZnO) the homology crystalline structure of expression, and satisfy the ratio of components of said scope 6.
11. the method for manufacture of each described sputtering target is characterized in that in the claim 4,5,6 and 8, comprises the operation of following (a)～(e):
(a) the starting compound powder is prepared the operation of mixture;
(b) said mixture is shaped and prepares the operation of the molding more than the thick 6.0mm;
(c) operation that atmosphere is heated up with the heat-up rate below 3 ℃/minute;
(d) the said molding that has heated up more than 2 hours below 96 hours, is obtained the operation of the above sintered compact of thick 5.5mm at sintering below 1520 ℃ more than 1280 ℃ again;
(e) operation of cutting more than the 0.25mm is ground on the surface of said sintered compact.
12. the method for manufacture of the described sputtering target of claim 5 is characterized in that, comprises the operation of following (a)～(e):
(a) the starting compound powder is prepared the operation of mixture;
(b) said mixture is shaped and prepares the operation of the molding more than the thick 6.0mm;
(c) operation that atmosphere is heated up with the heat-up rate below 3 ℃/minute;
(d) with the said molding that has heated up again surpassing sintering below 1350 ℃ and 1540 ℃ more than 2 hours below 36 hours, obtain the operation of the above sintered compact of thick 5.5mm;
(e) operation of cutting more than the 0.25mm is ground on the surface of said sintered compact.
13. the method for manufacture of the described sputtering target of claim 8 comprises the operation of following (f)～(i):
(f) the starting compound powder is prepared the operation of mixture;
(g) said mixture is shaped and is prepared into the operation of body;
(h) operation that atmosphere is heated up with the heat-up rate below 10 ℃/minute;
(i) with the said molding that has heated up again in the operation below 96 hours more than 4 hours of sintering below 1350 ℃ more than 1100 ℃.
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